Composition for disinfecting and other purposes.



UNITED STATES PATENT OFFICE.

LUDWIG HEINRICH REUTER, OF TOMPKINSVILLE, NEW YORK.

COMPOSITION FOR DISINFECTING AND OTHER PURPOSES.

1,027,000. i No Drawing.

To all whom it may concern.-

Be it known that I, Lnnwro H. REUTER, a citizen of the United States,residing at Tompkinsville, in the county of Richmond, borough ofRichmond, city of Greater New York, and State of New York, have inventeda new and useful Composition for Disinfecting and other Purposes, ofwhich the following is a specification.

My invention relates to a composition for disinfect-ing and otherpurposes in the form of a solution having valuable properties, useful inthe arts and for agricultural and hygienic purposes, and obtainable bycombining formaldehyde with alkali borate or rosin or preferably bot-h,and it includes what I regard as a new chemical compound formed andcontained in such compositions .which appears to be a condensationproduct of formaldehyde with abietic acid, the an hydrid of the latterbeing the principle constituent of the commercial rosin.

The composition which is the subject of my invention differs from allother products of that kind in so far as it does not contain anycarbonate or caustic alkali, such as is contained, for instance, in thearticle creolin; and no carbonate nor caustic alkali is used in itsmanufacture. Furthermore, my composition does not contain any free acidsuch as, for instance, formic acid which is found invariably in thecommercial formaldehyde solution of the market; the free formic acidcontained in the formaldehyde used in my preparation having beeneliminated by means of the alkali borate, which even if present inexcess does not-like caustic alkalis-produce any oxidizing effect onformaldehyde and does not, like ammonia, combine with formaldehyde andproduce basic bodies of undesirable properties.

-It is well known that rosin, being impure anhydrid of abietic acid, isinsoluble in water; it is equally known also that rosin dissolves inconcentrated caustic alkalis and yields a strongly caustic and alkalinerosin soap being contained up to 40% in the so-called creolin of themarket. I find by experiment that rosin is practically insoluble also inwater containing more or less formaldehyde gas.

Now I have discovered that formaldehyde solution if properly combinedwith rosin and alkali borate yields a perfectly clear solution, whichcan be mixed with water in all proportions without separationSpecification of Letters Patent.

Application filed August 13, 1906.

Patented May 21, 1912.

Serial No. 330,440.

of the rosin and without crystallization of the excess of alkali borateused. I will therefore describe a practicable way of carrying out thisprocess for producing the above mentioned chemical compound andcomposition. For instance, 250 lbs. of an alkali borate, as borax, '50lbs. of rosin and about 125 gallons of water are boiled together orheated in an autoclave under pressure, and a clear liquid is obtained,which if allowed to cool down to ordinary temperature (+15 to +25 C.)will separate not only the rosin but also the excess of alkali borate,of the 250 lbs. of alkali borate,

of which one part is soluble only in twenty parts of water of 15 0., 50lbs. will remain in solution, while 200 lbs. will separate in crystalform; at the same time also the rosin will be separated.

To the above mentioned solution comprising about 250 lbs. of alkaliborate, about 50 lbs. of rosin and about 125 gallons of water, whilestill warm-a 40 per cent. formaldehyde solution of the market is addedin small quantities at a time, while stirring. The liquid becomes cloudyat first but by and by it becomes perfectly clear after about 500 lbs.of the formaldehyde solution have been added; a perfectly stable liquidis obtainable, for instance, if to the warm solution of 250 lbs. ofalkali borate and 50 lbs. of rosin in 125 gallons of water, about 1300lbs. of the 40% formaldehyde solution are added. The same result isobtained by heating 250 lbs. of alkili borate, 50 lbs. of rosin and 235gallons of water and passing into the solution 520 lbs. of formaldehydegas; or by heating 250 lbs. of alkali borate, 50 lbs. of rosin, 225gallons of water and that quantity of trioxymethylene orparaformaldehyde, which is proportionate to 520 lbs. offormaldehyde-under pressure in an autoclace to a temperature of about150 C. When ordinary commercial trioxymethylene or paraformaldehyde areused it is necessary to ascertain how much formaldehyde gas a weightquantity, say 5 grams, will yield by heating with 100 cc. of water in apressure flask, as both articles are by-products in the formaldehydemanufacture and are never that weakly alkaline reaction, which is due tothe presence of the absolutely harmless alkali borate. The alkaliborate, serves as a two fold permanent protection for the formaldehyde,first, it neutralizes completely the free formic acid, and, secondly, ithas the tendency to protect the formaldehyde from becoming polymerizedand converted into pa'raformaldehyde, which is practically worthless asinsecticide, antiseptic and disinfectant or for waterproofing purposesin the textile and paper industry, or as an addition to waterproofpaints; for instance, to cold water paints containing casein.

As stated above the liquid composed as described can be mixed in allproportions with water above zero centigrade without separation of therosin, but when macerated with warm water is split up into formaldehydeand abietic acid. I have found that the liquid, if cooled down belowzero does not separate any alkali borate, though containing it in theproportion of one part to ten parts of the liquid, while 1:20 is knownto be the solubility limit at +15 C. But while no alkali boratecrystallizes from the liquid I' have found that at zero a semiliquid,brownish yellow, transparent mass settles to the bottom, which Iconsider as being a condensation product of abietic acid withformaldehyde. If the ice cold liquid standing above that mass is removedand water of +15 C. added, the mass is converted immediately into afiocculent whitish substance which, though being insoluble in water,redissolves in the liquid from which it has been removed which containsan excess of borax and formaldehyde.

I do not wish to limit myself to above mentioned proportions; viz: to apreparation containing 250 lbs. of alkali borate, 50 lbsof rosin, 125gallons of water and 1300 lbs. of the 40% formaldehyde solution, asvarious combinations will yield products, desirable and suit-able forspecial purposes, which fall within the scope of my invention. It may bedesirable, for instance, to use a large quantity of rosin, say, insteadof one part of rosin for five parts of alkali borate. one part of rosinfor 23 or 3.5 parts of alkali borate; also in this case clear liquidsare obtained, but if these liquids are mixed with water, more or lessopalescent or milky solution will be obtained containing part of therosin-formaldehyde condensation prod uct in finely suspended form. Sucha liquid I found very useful as insecticide for spraying plants orshrubs, corn, cotton, etc., which are infested with insects of the mostdestructive character; the finely suspended rosinformaldehydecondensation productwhen used as spray sticks to the plant, etc., and

prevents the rapid volatilization of the free formaldehyde. The effectis much .more energetic and lasting than that obtainable with ordinaryformaldehyde and in no instance was any injurious effect upon flowerbeds or cotton squares observed, While a good deal of damage resultedfrom the use of the acid formaldehyde of the market or from stronglyalkaline creolinsolution, etc. The insecticidal effect of therosin-formaldehyde condensation productnot only upon plants, but alsoupon wool or sheep, upon cattle, dogs and horses was very remarkable andit was found also to be an ideal means for dressing Wounds as anantiseptic and also for disinfecting purposes. Such a preparationcontaining more rosin is obtained by heating, for instance, 250 lbs. ofalkali borate, 80 lbs. of rosin and 125 gallons of water and adding tothe warm solution 13251330 lbs. of the .t0% formaldehyde solution. Thesame results are obtained by heating 250 lbs. of alkali borate, 75-80lbs. of rosin, 225 gallons of water and a quantity of trioxymethylene or'paraformaldehyde proportionate to 520 lbs. of formaldehyde gas in anautoclave to a temperature of 150 C. or over. Also this preparation isperfectly clear when finished and it shows, like the first-mentionedpreparation containing less rosin, a weakly alkaline reaction due to thealkali borate. also be used, as sodium,potassium, or lithium borate. Insome cases also the addition of soap, alcohol or glycerin or ofessential oils, like eucalyptus may be desired and I have found thatsuch additions improve the efiiciency of the preparation if used forspecial purposes. For instance a small percentage of soap or glycerinhas been found,

to be of advantage when the liquid is used for spraying purposes byfarmers, cotton growers, etc., as soap and glycerin, like alkali borate,protects the formaldehyde from becoming polymerized and oxidized.Continuing my investigations on that subject, I have discovered that ifto a liquid containing in 100 lbs. about 30 lbs. of soft (potash) soapor 30 lbs. of hard (soda) soap prepared from oils or fats containingprincipally glycerids of oleic or ricinoleic acid and the like and20lbs. of formaldehyde gas, 7'

about 10 lbs. of rosin are added and the mixture digested, whilestirring at a temperature of +40 to +50 0., a clear liquidis obtained,which contains in addition to the soap and to an excess of formaldehydea condensation product of rosin with formaldehyde. This new preparationkeeps clear at ordinary temperature, say at +15 to +25 O.,but onexposing it for some time to zero temperature part of therosin-formaldehyde condensatlon product, separates, but redissolves assoon as the liquid has assumed,

again ordinary temperature. On mixing the new preparation with watersome of the con- V densation product is precipitated in fioccules andthe solution consequently does not possess that uniform appearance,which is obtained when the preparation, free from soap, but containingalkali borate and fully described above, is dissolved in water.

Now I have discovered, that a combination of soap, rosin andformaldehyde, dissolving well in all proportions in water, is obtained,if an excess of alkali borate is added. This new preparation can beobtained as follows: About 30 lbs. of soft (potash) soap, or 30 lbs. ofhard (soda) soap, prepared from oils or fats containing glycerids ofoleic or ricinoleic acidare dissolved in 50 pints of water and 20 poundsof formaldehyde gas passed into the soap solution at a temperature ofabout 0., while stirring. Then 10 pounds of rosin are added and thedigestion of the mixture continued,

until all the rosin is dissolved, then I add a mixture, which has beenprepared by dissolving about 25 lbs. of alkali borate in a liquidcomprising about pints of water and about 20 pounds of :t'ormaldehydegas.

I continue to stir and to digest untillthe liquid presents a uniformmixture, which yields, when mixed with water a clear liquid, whichbecomes opalescent if standing for a couple of hours and milky white ifstanding for a couple of days, but without precipitating thecondensation product in floceules. A liquid of this character andcontaining soap,

free formaldehyde, alkali borate and the condensation product, I havefound to be useful for agricultural and hygienic purposes, inasmuch asit does not contain any free caustic alkali, as it is contained increolin or other similar coal tar products.

The superior efliciency of my preparation is due to a large extent tothe condensation product, which covers the plants and isthanks to acontinuous development of small quantities of formaldehyde, disliked byall insects. Also as a general disinfectant and antiseptic I have foundmy new preparation superior to other formaldehyde preparations of themarket, inasmuch as, when the 40'per cent. formaldehyde solution of themarket has been used in its manufacture, the free formic acid, alwayscontained therein, has been entirely neutralized by the alkali borateand my preparation does not develop consequently irritating effects, dueto formic acid. At the same time the condensation product covers thewound and constantly developing small quantities of formaldehyde, itsefiiciency is not temporary but lasting.

The method of preparation as well as the proportions can be varied,within the scope of my claims. For instance instead of passingformaldehyde gas into the solutions a proportionate quantity of the 40per cent. formaldehyde solution of the market can be used, alsotrioxymethylene and paraformaldehyde can be used in proportion, but inthis case the materials have to be heated under pressure in an autoclaveat a temperature of not below 150 0., to be sure, that the polymerizedcompounds are properly converted into formaldehyde gas and dissolved.

Instead of dissolving the rosin in the soap, itcan be dissolved also inthe alkali borate solution as described above, or in the formaldehydesolution. I wish to state also, that instead of commercial rosin, anysubstance which yields abietic acid, as for example 'purified or pureabietie acid may be used.

Any alkali borate can be used, such as lithium, potassium, or sodiumborate, but in practice the cheapest namely, sodium borate or borax ispreferable.

Instead of using a composition comprising 30 lbs. of soap, 10 lbs. ofrosin, 40 lbs. of formaldehyde gas, 25 lbs. of alkali borate and 110pints of water, also more or less soap can be taken; if a liquid isdesired yielding with water a mixture containing more of thecoiulensation product in finely suspended form. then, instead of 10 lbs.of rosin more, for instance, 15 lbs. can be used. Another way ofproducing the preparation is the following. 330 lbs. of a liquid,obtained by digesting together about 30 lbs. of rosin, about lbs. offormaldehyde gas, about 90 lbs. of soap and about 150 pints of water, ismixed with 41:50 lbs. of a liquid containing about 150 lbs. of alkaliborate, 90 lbs. of soap, 60 lbs. of formaldehyde gas and 1.50 pints ofwater; the mixture is digested for 34; hours; also this liquid mixeswith water in all proportions.

Having thus fully described my invention, what I claim and desire tosecure by Letters- Patent is:--

l. A composition comprising a solution of formaldehyde, alkali borate,and a substance which at zero centigrade is a semi-liquid,brownish-yellow, transparent mass, which is insoluble in water butmiscible therewith in all proportions above zero centigrade withoutseparation of the ingredients, which is soluble in water containingborax and formaldehyde, and which when macerated with warm water issplit up into formaldehyde and abietic acid.

2. A composition comprising a solution'of formaldehyde, alkali borate,soap, and a substance which at zero centigrade is a semiliquid,brownish-yellow, transparent mass which is insoluble in water butmiscible therewith in all proportions above zero centigrade withoutseparation of the ingredients, which is soluble in water containingborax and formaldehyde, and which when macerated with warm water issplit up into formaldehyde and abietic acid.

3. A composition comprising a solution of formaldehyde, alkali borate,potash soap, and a substance which at zero centigrade is a semi liquid,brownish yellow, transparent mass which is insoluble in waterbutmiscible therewlth 1n all proportions above Zero centigrade withoutseparation of the ingredients, which is soluble in water containingboraX and formaldehyde, and which when macerated with warm water issplit up into formaldehyde and abietic acid.

4:. A composition comprising a solution of formaldehyde,borax, and asubstance formed from abietic acid and formaldehyde which at zerocentigracle is a semi-liquid, brownishyellow mass which is insoluble inwater but miscible therewith in all proportions above zero Centigradewithout separation of the ingredients, which is soluble in watercontaining borax and formaldehyde, and which when macerated with warmwater is split up into formaldehyde and abietic acid.

5. A composition comprising a solution of formaldehyde, boraX, potashsoap, and a sub stance formed from abietic acid and formaldehyde whichat Zero centigrade is a semi liquid, brownislryellow mass which isinsoluble in water but miscible therewitl'i in all proportions aboveZero Centigrade without separation of the ingredients, which is solublein water containing borax and formaldehyde, and which when maceratedwith warm water is split up into formaldehyde and abietic acid.

6. A composition comprising a solution of formaldehyde, borax, soap, anda substance formed from abietic acid and formaldehyde which at zerocent-igrade is a semi-liquid, brownish-yellow mass which is insoluble inwater but miscible therewith in all proportions above zero Centigradewithout separation of the ingredients, which is soluble in watercontaining borax and formaldehyde, and which when macerated with warmwater is split up into formaldehyde and abietic acid.

7. A process of making a composition for antiseptic and disinfectingpurposes and the like, which comprises the treatment with formaldehyde,of a mixture of alkali borate and rosin substantially as described.

8. A process of making a composition for antiseptic and disinfectingpurposes and the like, which comprises the treatment with formaldehydeof a solution of alkali borate, soap, and a substance yielding abieticacid substantially as described.

9. A processof making a composition for antiseptic and disinfectingpurposes and the like, comprising the treatment with formaldehyde, of asolution of alkali borate, and a substance comprising abietic acid toproduce a composition which at zero centigrade precipitates asemi-liquid brownish yellow mass, substantially as described.

10. A composition ofmatter comprising a solution of formaldehyde, alkaliborate, soap, and a substance which at Zero Centigrade settles to thebottom of the solution as a semiliquid brownish yellow mass, and whichif the liquid above it be removed and water at about 15 centigrade beadded is thereby converted into a flocculent whitish substance which isinsoluble in water, but which redissolves in the liquid from which ithas been removed and which when macerated with warm Water yieldsformaldehyde and abietic acid,

11. A process of making a composition for antiseptic and disinfectingpurposes and the like, which comprises a treatment with formaldehyde, ofa solution of alkali borate, rosin and soap.

In testimony whereof I have hereunto set my hand, in the presence of twosubscribing witnesses.

LUDl/VIG HEINRICH REUTER. Witnesses FLoRnNon G. SHIELDS,

AUGUSTA SIEMANN.

Copies of this patent may be obtained for five cents each, by addressingthe Commissioner of Patents.

Washington, D. G.

